Hair treating composition and process



'tially linear water-soluble polymer,

United States Patent 3 178 353 HAIR TREATLNG COlVlPSITION AND PROCESKarlheinz Scheller, Schillcrstrasse 25-27, and August lilodcnsielr,Konigstrasse 38, both of Eislingen (Fils),

Germany No Drawing. Filed July 18, 1960, Ser. No. 43,284 Claimspriority, amendment of Nov. 2, 1957, application Germany, June 24, 1957,Sch. 22,344 16 Claims. (Cl. 167-87) This application is acontinuation-impart of our application Serial No. 770,912, filed October31, 1958, now abandoned.

The invention relates to the manufacture of a prepara tion for thetreatment of hair and hair bearing epithelium, which preparation istherefore suitable for treating the hair of the head and beard, forexample before using an electric razor. it is for example known to usehair tions, hair fixatives, setting creams, liquids containing alcohol,such as Eau de Cologne, and similar preparations for these purposes. Byhair lotion is understood a per- (fumed alcoholic liquid which isdiluted with water and which can contain certain additives fornourishing the hair and hair-bearing epithelium such as glycerine,lecithin, cholestrin and patent extracts, for example camomile andnettles.

By setting creams are understood perfumed emulsions of the water-in-oilor oil-in-water type, which in addition to the additives used in hairlotions, can also contain additives which make the hair suitable forwaving, impart gloss thereto and enable the Waves to last for arelatively long time.-

. By hair fixative is understood pleasantly perfumed and usually aqueoussolutions, primarily of substances which impart a thinnest possiblelustrous film to the hair, this V film holding the hair for a certaintime in the required setting, for example, polyvinyl alcohol, alkalialginate, tragacanth, tylose (carboxymethyl cellulose).

The invention is concerned with a universal agent for the treatment andcare of the hair, this agent having the surprising and novel'property ofcombining the effects of known treating agents, such as hair lotions,setting creams and hair fixatives, and being at the same time in such aform that it can be packed in tubes and consequently can be easilyhandled.

The agent according to the invention for the treatment and care of hairand hair-bearing epithelium contains an alcoholic gel of a synthetic,insoluble, lightly cross-linked carboxylic. polymer in addition to atleast 40% of alcohol, and is in the form of a paste or jelly.

The lightly cross-linked carboxylic interpolymers which are useful forpreparing the products of this invention are described in U.S. PatentsNos. 2,798,053 and 2,858,- 280. The carboxylic acid component ofinterpolymers can be defined as an alpha-beta monoolefinicallyunsaturated acid.1 This includes monomers such 'as acrylic acid,methacrylic acid, ethacrylic acid, alpha-phenyl acrylic acid, crotonicacid, beta-acryloxy. propionic acid,.

hydrosor-bic acid, sorbic acid, cinnamic acid, beta-styryl acrylic acid,hydromuconic acid,itaconic acid, citraconic acid, mesaconic acid,muconic acid, glutaconic acid, angelic acid, umbellic acid, maleic acid,fumaric acid and maleic anhydride.

It is known that maleic acid, fumaric acid, the betasubstituted acrylicacids and maleic anhydride will not homopolymerize to produce highmolecular weight polymers and so when such acids are employed it isessential to use an additional monomer which will either homopolymerizeor which will copolymerize with the maleic acid, furnaric acid or maleicanhydride to form an essen- The comonomers which will copolymerize withmaleic acid, fumaric acid or maleic anhydride include suchmonoolefinically un- 3,173,353 Patented Apr. 13, 1-965 ice saturatedmonomers as alkyl vinyl ethers having from 1 to about 8 carbon atoms inthe alkyl groups, acrylic acid, methacrylic acid, ethacrylic acid,acrylonitrile, acrylamicle, N-alkyl acrylamide, N,N-dialkyl acrylamidein which the alkyl groups have from about 1 to 12 carbon atoms,methacrylonitrile, acrylate ormethacrylate esters of lower monohydricalkanols having about 1-8 carbon atoms, ethylene, isobutylene, butylene,styrene, vinyl esters of lower saturated aliphatic carboxylic acids,having from 1 to about 8 carbon atoms, vinyl benzoate, vinyl chloride,vinylidene chloride, vinyl pyridine, vinyl carbazole and othermonoolefinic monomers which are known to copolymerize with the maleic orfumaric acids or maleic anhydride to form linear polymers.

The homopolymeriza-ble acids, such as acrylic, methacrylic or otheralpha lower alkyl substituted acrylic acids can also be used inadmixture of at least 50 mole percent by weight of such acid with theother monomers mentioned above.

Mixtures of homopolymerizable acids can be used in any proportion.

The cross-linking agents are those which have an average of more than 2terminally unsaturated vinylidene groups on the molecule. These includecompounds such as the polyunsaturated ethers described in U.S. PatentNo. 2,798,053 and the solvent-soluble diene polymers or copolymershaving a plurality of vinylidene or vinyl side chains, as described inU.S. Patent No. 2,858,281.

These polyunsaturated ethers are polyalkenyl polyethers of polyhydricalcohols containing more than one alkenyl group per molecule, the parentpolyhydricalcohol containing at least 4 carbon atoms and at least threehydroxyl groups. The alkenyl group has a terminal CH =C structure andcontains from 2 to 4 carbon atoms. Thus, the alkenyl group can be vinyl,allyl or methallyl.

The polyhydric alcohol can be a butane tn'ol, a tetrose, pentose orhexose sugar, an aligasaccharide, reduced derivatives of said sugars,often termed sugar alcohols, or a sugar acid.

The cross-linking agents of U.S. Patent 2,858,281 are soluble insolvents such as benzene and are made by polymerizing a monomericconjugated diene hydrocarbon or a mixture containing at least 50% of aconjugated diene hydrocarbon and another monomer polymerizable with thediene in an inert solvent with an alkali metal catalyst. Representativedienes are butadiene-l,3, isoprene, piperylene and1,2-dimethylbutadiene. Representative comonomers include styreneacryloni-trile, methyl methacrylate, methyl acrylate, vinylidenechloride and vinyl pyridine. This class of homo and copolymers has ahigh proportion of residual saturation present as vinyl side chains.

The amount of cross-linking agent used will vary somewhat depending onthe proper-ties desired in the final interpolymer, but usually from 0.1to about 5% by weight of the combined weight of the other monomers, ofwhich at least 50 mole percent is a carboxylic monomer. T he remaining50 mole percent of the monomer mixture is immaterial, and if ahomopolymerizable carboxylic acid or a mixture of such acids is used,then only the crosslinking agent and the said acid or mixtures thereofneed be used. 7 I

The preferred canboxylic acid monomer is acrylic acid and the preferredcross-linking agent is a polyallyl sucrose having from 5 to 6 allylgroups per sucrose molecule. The preferred range of acid tocross-linking agent is 98- 99% of acid and 1.0 to 2.0% cross-linkingagent.

Especially suitable alcohols for use in the agent according to theinvention are low aliphatic alcohols, such as ethyl or isopropylalcohols or other liquid physiologically acceptable alcohols. Otherconventional substances for a nourishing the scalp or promoting hairgrowth can be added to the hair-treating agent. 'Thus for examplestearins such as cholesterine, phosphatides, for example lecithin,pantothenic acid or others, as well as for example perfumes and the likecan be added to the alcohols. On the other hand, greasing and softeningagents, such as glycerine, glycol or castor oil, can be added to theaqueous solutions of the gel-forming substances.

For the production of the agent for treating hair, such as beard or headhairs, and hair-bearing epithelium the gel-forming substance isintroduced into a liquid mixture containing water and at least 40% ofalcohol, and left to swell for a sufficient time, for example overnight.The gel former in this case is a finely divided powder, which can easilybe dispersed in the water-alcohol mixture, for example by stirring.

As is usual with the swelling of gel formers, an acceleration of theswelling process can be obtained by mechanical movement during theproduction of the jelly, i.e. during the swelling. After the gel formerhas been swelled, it is advisable to stir again thoroughly andthereafter to neutralize the gel with the necessary quantity of a basiccompound. Physiologically unobjectionable basic compounds, such as thosewhich have for example previously been used in the cosmetic art, aresuitable for this neutralization. As examples, there are mentionedalkali and alkaline earth carbonates, amines, such as triethanolamineand especially fatty acyl alkylol amides.

Surprisingly, it was found that the described acid amides can serve toneutralize or form an addition compound with carboxylic polymers whichforms a clear gel in a mixture containing a very high alcohol content.This activity is surprising because the NH group in the amide isessentially neutral, and has lost much of its basic character because ofits attachment to the group. Indeed, it is known that amides areunstable in the presence of mineral acids and that they are subject tohydrolytic cleavage in such systems. It was therefore unexpected thatthe fatty acid amides would thicken a mucilage of the cross-linkedacidic interpolymers to form a firm gel in an aqueous mixture containingat least 40% alcohol by forming addition compounds with or neutralizingthe polymer.

Typical fatty acyl alkylol amides are those obtained by reacting fattyacids from natural fats or mineral or vegetable oils with an alkylolamine having at least one replaceable hydrogen on the nitrogen atom. Thefatty acids contain from 8 to about 18 carbon atoms or more particularlyfrom about 12 to 18 carbon atoms.

Representative amino alcohols that can be reacted with the fatty acidsare mono-ethanol amine, diethanol amine, monopropanol amine, dipropanolamine, monoethanol monopropanol amine, or other monoor dialkanol aminesin which the alkanol has from 2 to about 4 carbon atoms. The amides havethe generic structure in which R is an aliphatic hydrocarbon radical offrom 7 to about 17 carbon atoms, R and R each represents hydrogen, analkylol or a polyalkylol group.

Concentrates of the N alkylol substituted fatty acid amides have beenused heretofore as foam stabilizers in shampoos. In the composition ofthis invention they supply fatty ingredients to the hair and scalp.

The amount of fatty acid amide can vary between about 0.5 and about 6.5%and particularly between about 0.75 and 5.0% based on the finishedproduct. If desired, small amounts of triethanolamine 0.1 to 0.2% basedon the finished product can be used in addition to the amide.

The amount of acidic interpolymer in the gel is relatively small and canvary between about 0.5 and 2% by weight of the finished product andpreferably 0.7 to about 1.5%. This small amount of polymer forms a verythin film on hair or scalp so that the residue after frequent andrepeated applications is not troublesome nor is it perceptible to touch.

The gel which is formed is clear, it gives a high gloss and is extremelystable.

By comparison with the prior known agents for hair treatment, the agentaccording to the invention in the form of a paste ofiers considerableadvantages. Since the agent is a paste which can be packed in tubes, thehandling thereof is extremely simple. By comparison with a hair lotion,it offers for example the advantage that it does not run out of badlysealed containers. Due to the high alcohol content, it has adisinfecting, astringent and refreshing action in the same way as aconventional agent with a high alcohol content for the treatment of theskin and the scalp. After evaporation of the liquid, the selected gelformer remains as a scarcely perceptible residue on the hair and on theskin. This residue is present in the form of a thin film, which has theproperty of not being brittle, but of being flexible and firmlyadhering, so that when it is used as a fixative for the hair of thehead, a comparatively large quantity of the hair treatment agent cangradually be applied between the individual shampoos without anypossibility of the hair being disturbed as a result of the gel formerwhich had been applied becoming detached because of breaking of thefilm. After the gel has been applied, the hair feels soft and silky andno sticky or other undesirable residues are left on the hands afterapplication. It is further shown that the agent according to theinvention for the treatment and care of the hair can be applied over anunlimited period without any secondary properties detrimental to the usethereof becoming apparent. Due to the film formed on the hair and thehair bed, the particular gel former imparts a high lustre to the hairand also gives the hairs a certain rigidity. When the hairs have forexample been brought to a particular position, they tend to remainpermanently in this position, so that the hair can be more easily andbetter curled, although the new agent does not have a greasy action.

When used as a shaving auxiliary, more especially before using anelectric razor, it is shown that the agent according to the inventionproduces a certain protection against mechanical irritation due to thefilm thereof formed on the skin. Due to the contracting action of thefilm, the surface of the skin is smoothed and the individual hairs ofthe beard are erected, whereby electric shaving can be carried out moreeasily. On the whole, a coherent and contracting film is produced, bywhich the difiiculties which usually arise with electric shaving areobviated. This greater strength makes it possible to shave more easily.

The novel agent for treating and caring for the hair consequentlycombines the action of the various hair treating agents, such as hairlotion, hair fixative and setting cream. The use of the new preparationalso makes the use of oil superfluous. Furthermore, the preparationoffers the advantage that it can be used as a frictional agent in thesame way as the known hair lotions.

It is known that water-containing jellies can be produced by the gelformer employed according to the invention. By adding relatively largequantities of alcohol, for example 20 to 35%, to such jellies with awater-base the gel former is precipitate. Thus it occurs in the form ofa solid lump which cannot be further employed and it is impossible inthis way to produce jellies with a relatively high alcohol content.Consequently, it is very surprising that it is possible by using theprocess according to the invention to produce gels with a high alcoholcontent which can in principle contain more than 40% of alcohol and ifdesired even or even more alcohol without the gel-forming properties ofthe gel former which is employed being thereby deleteriously affected.On the other hand, it has been found that these gels with a high alcoholcontent are clear, stable products which give a high gloss and areexcellently suitable for the purposes according to the invention.

The invention is further illustrated by. the following non-limitingexamples:

Example I 1% of an interpolymer of 99% glacial acrylic acid and 1% allylsucrose containing an average of about 5.8 allyl groups per sucrosemolecule is added while stirring to a normal hair lotion consisting forexample of 50% of isopropyl or ethyl alcohol, 47% of water and 3% ofperfume Example 11 1 g. of the polymer described in Example I was addedto 74 g. of a perfumed water-isopropanol mixture containing about 56%-by volume of the alcohol and then allowed to swell. To the mucilage wasadded a solution of 3 g. of coconut oil diethanol amide in 22 g. of theabove-described water-isopropanol mixture, while the mucilage is stirredvigorously. There results 100 g. of a clear and consistent gel.

Example III A mucilage made from 0.75 g. of the polymer of Example I and74.25 g. of a perfumed water-isopropanol mixture containing about 56% byvolume of the alcohol was mixed, by the procedure described in ExampleH, with 0.75 g. coconut oil polydiethanol amide dissolved in 24.25 g. ofthe water-isopropanol mixture described above. There resulted 100 g. ofa gel form of hair treating material.

Example IV 75 g. of the mucilage described in Example II were mixed witha'solution of g. of lauric acid diethanol amide in g. of the describedwater-isopropanol mixture and stirred vigorously for a short time. Thereresulted a clear very viscous gel which is particularly useful fortreating dry and difliculty curlable hair.

Example V A mucilage containing 0.75 g. of the polymer of Example II in74.25 g. of a perfumed water-ethanol mixture containing about 55% byvolume of the alcohol, was mixed in the manner described in Example IIwith a solution of 0.13 g. of triethanolamine and 1.5 g. of coconut oilacid diethanolamide dissolved in 23.37 g. of the water-ethanol mixture.There were obtained 100 g. of a clear gel form of hair dressingmaterial.

It is to be understood that the other hydrophilic carboxyl containing,lightly cross-linked interpolymers can be substituted within the rangeof 0.5-2% by weight of the finished compositions of this invention toobtain gel forms of hair treating material. Thus, acrylic acidcrosslinked with polyallyl pentaerythritol, allyl sorbitol, allylraflinose, allyl inositol or a polybutadiene polymerized in apredominantly 1,2 structure can be substituted part for part in theabove examples. Also, acrylic acid, methacrylic acid interpolymerslightly cross-linked with the cross-linking agents can be sosubstituted. In addition, interpolymers of the acrylic acid maleic acidor anhydride or fumaric acidplightly cross-linked as described, can beused in place of the polymers of the examples. Among the lightlycross-linked interpolymers made from maleic anhydride and anothermonomer that is copolymerizable therewith in substantially equimolarproportions those which are specially useful in this invention are themaleic anhydride-ethylene and maleic anhydride isobutylene cross-linkedinterpolymers.

We claim:

1. An agent for the treatment of hair and hair bearing epithelium, whichcomprises an aqueous-alcoholic gel of from about 0.5 to about 6.5% basedon the weight of the finished composition of (A) an interpolymer of (l)at least 50 mol percent of an alpha-beta, monoolefinically unsaturatedcarboxylic'acid having from 3 to 10 carbon atoms and from 0 to 50 molpercent of a different monoolefinically unsaturated monomercopolymerizable with said acid and (2). from 0.1 to about 5% by weight,based on (1) of a cross-linking agent selected from the class consistingof (I) a hydrocarbon soluble alkali metalcatalyzed homopolymer of abuta-diene-1,3 and .(II) polyalkenyl polyethers of polyol-s having atleast 3 hydroxyl groups and at least 4 carbon atoms, said polyalkenylgroups being present on the average of more than 2 per polyol moleculeand being terminally unsaturated vinylidene groups of from 2 to 3 carbonatoms, and (B) at least 40% and up to 70% by weight based on the weightof the finished composition of a liquid physiologically acceptable lowermonohydric alcohol, the said composition being neutralized to a pH of atleast 6 with at least one member selected from the class consisting oftriethanolamine and an amide of the structure R1 Rlhs in which R isaliphatic hydrocarbon of from 7 to ;17 carbon atoms and R and R each isselected from the class consisting of hydrogen, an alkylol group and apolyalkylol group.

'2. The composition of claim 1 in which the crosslinking agent in theinterpolymer is allyl sucrose containing an average of from 5 to 6 allylgroups per sucrose molecule.

3. The composition of claim 1 in which the interpolymer consists oftrout 98-99% by weight of acrylic acid and l to 2% by Weight of allylsucrose having an average of from 5 to 6 allyl groups per sucrosemolecule.

4. The composition of claim 1 in which the interpolymer consists ofsubstantially equimolar quantities of (A) maleic anhydride and (B)isobutyle-ne cross-linked with (C) from about 1 to 5% by weight based onthe combined weight of (A) and (B) of a solvent soluble sodiumpolymerized polybutadiene.

5. The composition of claim 1 in which the interpolymer consists of from98 to 99% by weight of acrylic acid and from 11 to 2% by weight ofallyllpentaerythritol containing an average of more than 2 allyl groupsper molecule.

6. The composition of claim 1 containing in addition at least one memberselected from the class consisting of stearins, phosphatides, glycerol,glycol and castor oil.

7. The composition of claim '1 containing from 0.5 to 2.0% based on theweight of the finished composition of the cross-linked intenpolymer.

8. The composition of claim 1 in which the monohydric alcohol is analkanol of from 2 to 3 carbon atoms.

9. A process for preparing an agent for the treatment and care of hairand hair bearing epithelium, which comprises adding the inter-polymer ofclaim 1 to a mixture of water containing at least 40% and up to 70% byweight of a liquid physiologically acceptable lower monohydric alcohol,allowing the interpolymer to swell -t-he-re in and thereafterneutralizing to a pH of at least 6 with a member selected from the classconsisting of triethanolamine and an amide of the structure 0 R1 R' N R2in which R is aliphatic hydrocarbon of from 7 to 17 carbon atoms and Rand R each is selected from the class consisting of hydrogen, 'analkylol group and a polyalkylol group.

10. The process of claim 9 in which the monohydric alcohol is an alkanolhaving from 2 to 3 carbon atoms.

11. The process of claim 9 which comprises elfecting neutralization byadding triethanolamine.

12. The process of claim 9 which comprises effecting neutralization byadding an amide of a fatty acid from 8 to 18 carbon atoms.

13. The process of claim 9 which comprises effecting neutralization witha fatty acyl alkylol amide.

14. The process of claim 9 which comprises effecting neutralization withcoconut oil diethanol amide.

15. The process of claim 9 which comprises effecting neutralization withcoconut oil polydiethanolamide.

a. 16. The process of claim 9 which comprises efiecting neutralizationwith lauric acid diethanolamide.

References Cited by the Examiner UNITED STATES PATENTS JULIAN S. LEVITT,Primary Examiner.

M. O. WOLK, FRANK CACCIAPAGLIA, In, IRVING MARCUS, Examiners.

1. AN AGENT FOR THE TREATMENT OF HAIR AND HAIR BEARING EPITHELIUM, WHICHCOMPRISES AN AQUEOUS-ALCOHOLIC GEL OF FROM ABOUT 0.5 TO ABOUT 6.5% BASEDON THE WEIGHT OF THE FINISHED COMPOSITION OF (A) AN INTERPOLYMER OF (1)AT LEAST 50 MOL PERCENT OF AN ALPHA-BETA, MONOOLEFINICALLY UNSATURATEDCARBOXYLIC ACID HAVING FROM 3 TO 10 CARBON ATOMS AND FROM 0 TO 50 MOLPERCENT OF A DIFFERENT MONOOLEFINICALLY UNSATURATED MONOMERCOPOLYMERIZABLE WITH SAID ACID AND (2) FROM 0.1 TO ABOUT 5% BY WEIGHT,BASED ON (1) OF A CROSS-LINKING AGENT SELECTED FROM THE CLASS CONSISTINGOF (I) A HYDROCARBON SOLUBLE ALKALI METALCATALYZED HOMOPOLYMER OF ABUTADIENE-1,3 AND (II) POLYALKENYL POLYETHERS OF POLYOLS HAVING AT LEAST3 HYDROXYL GROUPS AND AT LEAST 4 CARBON ATOMS, SAID POLYALKENYL GROUPSBEING PRESENT ON THE AVERAGE OF MORE THAN 2 PER POLYOL MOLECULE ANDBEING TERMINALLY UNSATURATED VINYLIDENE GROUPS OF FROM 2 TO 3 CARBONATOMS, AND (B) AT LEAST 40% AND UP TO 70% BY WEIGHT BASED ON THE WEIGHTOF THE FINISHED COMPOSITION OF A LIQUID PHYSIOLOGICALLY ACCEPTABLE LOWERMONOHYDRIC ALCOHOL, THE SAID COMPOSITION BEING NEUTRALIZED TO A PH OF ATLEAST 6 WITH AT LEAST ONE MEMBER SELECTED FROM THE CLASS CONSISTING OFTRIETHANOLAMINE AND AN AMIDE OF THE STRUCTURE